CN102569896B - Lithium ion secondary battery and preparation method thereof - Google Patents
Lithium ion secondary battery and preparation method thereof Download PDFInfo
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- CN102569896B CN102569896B CN201010601263.XA CN201010601263A CN102569896B CN 102569896 B CN102569896 B CN 102569896B CN 201010601263 A CN201010601263 A CN 201010601263A CN 102569896 B CN102569896 B CN 102569896B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract
The invention provides a preparation method of a lithium ion secondary battery. The method comprises the following steps of: accommodating a battery pole in a battery shell; injecting non-aqueous electrolyte into the battery shell; and performing charging formation and then sealing the battery shell in which the non-aqueous electrolyte is injected, wherein the non-aqueous electrolyte contains one or more additives; the one or more additives are one or more of aniline monomers and pyrrole monomers; the charging formation comprises one or more constant current charging processes; at least one charging current in the constant current charging is 0.001-0.05 C; and the cut-off voltage of the charging formation is 3.6-4.2 V. The invention also provides the lithium ion secondary battery prepared by the method provided by the invention. The lithium ion secondary battery prepared by the method provided by the invention has superior high-power discharge performance. The method according to the invention is simple and practical and is easy for realizing large-scale production.
Description
Technical field
The present invention relates to a kind of lithium rechargeable battery and preparation method thereof.
Background technology
Lithium rechargeable battery has that voltage is high, memory-less effect, energy density are high and the feature such as good cycle, is thus widely used.
In general, the quality of battery performance depends on electrode material.There is the positive electrode mainly various transition metal oxide of the lithium rechargeable battery of actual application value at present, these materials all belong to insertion-host electrode materials, ubiquity electron conduction is poor, the problem that lithium ion diffusion rate is low, thus makes the high power discharge ability of corresponding lithium ion battery.Preparation method from lithium ion secondary battery electrode: because the ionic conductivity of insertion-host electrode materials is poor, for obtaining ideal electrical property, generally needs when preparing electrode to add a certain amount of conductive agent (such as: carbon black, graphite).In addition, in order to meet the needs of machine-shaping, traditional electrode production process also needs to add a certain amount of binding agent (such as: Kynoar and polytetrafluoroethylene).These binding agents all belong to insulating properties material, therefore need more conductive agent to meet the demand of battery discharge.But the conductive agent with high-specific surface area needs to use more binding agent, to meet the needs of machine-shaping.Because conventional conductive agent and binding agent all do not possess electro-chemical activity, final result is that electroactive substance relative quality is in the electrodes lower, this have impact on the actual specific capacity of electrode integral to a great extent, and simultaneous electrochemical active material content in the electrodes and deployment conditions also can affect the high power discharge performance of battery.
Poor for insertion-host electrode materials electron conduction, lithium ion diffusion rate is low, cause the problem of the high power discharge performance deficiency of battery, people mainly take following technical measures: the particle diameter 1, reducing material, and preparation sub-micron or nano material reduce the diffusion length of lithium ion; 2, Surface coating (as carbon is coated, nano metal or nano-metal-oxide coated); 3, element doping is (as LiFePO
4li position, Fe position, P position, O position doping).Although these methods can improve the electric conductivity of electrode material to a certain extent, but still exist a lot of dead " lithium ", the capacitance loss of lithium rechargeable battery still exists, and the high power discharge performance of lithium rechargeable battery is affected.
Summary of the invention
The object of the invention is to the electronic conductance rate variance overcoming the electrode material in existing lithium rechargeable battery, cause the defect of the high power discharge performance deficiency of battery, there is provided a kind of method preparing lithium rechargeable battery, the electrode material in lithium rechargeable battery obtained by this method has electronic conductivity and the high power discharge performance of raising.
The present inventor finds in research process, although by adding the electric conductivity that conducting polymer can improve lithium ion secondary battery anode material to a certain extent in positive electrode active materials, battery still can not be made to have gratifying high power discharge performance.Its reason may be because conducting polymer is organic polymer, and positive electrode active materials is generally inorganic compound, the compatibility of the two is poor, therefore conducting polymer is being mixed with positive electrode active materials and slurrying, and the slurry obtained is coated to plus plate current-collecting body carries out drying or calendering process in, conducting polymer is very easily reunited, and causes the distribution of conducting polymer in positive electrode active materials very uneven, so that can not significantly improve the high power discharge performance of battery.And, improving the electronic conductivity of lithium rechargeable battery and the effect of high power discharge performance to obtain, usually needing to use relatively large conducting polymer.
CN101145622A discloses a kind of reversible over-charge protective electrolyte additive for lithium ion battery, and described additive is one or more in aromatic aniline, diphenylamines, triphenylamine, pyrroles, thiophene, diphenyl sulfide and benzene.The CN101145622A preparation method of lithium rechargeable battery also disclosed containing above-mentioned additive in electrolyte comprises and being changed into the electric current of 50mA (that is, 0.09C) by battery.But the present inventor finds in research process, the high power discharge performance of the lithium rechargeable battery that disclosed in CN1385918A prepared by method is also unsatisfactory.
The present inventor finds through further investigation, the monomer that can form conducting polymer under electrochemical conditions is added in the nonaqueous electrolytic solution of lithium rechargeable battery as additive, carry out charging by using the lithium rechargeable battery small area analysis of this nonaqueous electrolytic solution to change into, then can improve the high power discharge performance of lithium rechargeable battery.This completes the present invention.
The invention provides a kind of preparation method of lithium rechargeable battery, the method comprises to be held Battery Pole Core in the cell housing, and nonaqueous electrolytic solution is injected in battery container, then the battery container of this injection nonaqueous electrolytic solution is carried out charging and change into rear sealing, wherein, described nonaqueous electrolytic solution contains additive, described additive is one or more in aniline system monomer and azole series monomer, described charging changes into and comprises one or more constant current charge, the charging current of at least one in this constant current charge is 0.001-0.05C, the cut-ff voltage that this charging changes into is 3.6-4.2V.
Present invention also offers a kind of lithium rechargeable battery prepared by method of the present invention.
Prepared according to the methods of the invention lithium rechargeable battery has excellent high power discharge performance, its reason may be: according in method of the present invention, described nonaqueous electrolytic solution contains the additive that oxidative coupling reaction can occur under electrochemical conditions, change in charging and comprise one or more constant current charge, and the charging current of at least one in this constant current charge is when being 0.001-0.05C, the additive be dissolved in nonaqueous electrolytic solution can move in the space between the positive electrode surface of battery and positive electrode active materials on plus plate current-collecting body, when charging voltage reaches the oxidizing potential of described additive, described additive generation in-situ oxidation coupling reaction, and then conducting polymer network is formed on the positive pole of lithium rechargeable battery, on the one hand by described additive is dissolved in nonaqueous electrolytic solution, in formation process, in-situ preparation conducting polymer on positive pole, can also effectively avoid directly by conducting polymer and positive electrode active materials mixed pulp to prepare positive pole time the extremely incident conducting polymer problem of reuniting, and the conducting polymer network formed thus can improve the conductivity of battery anode active material effectively, the conducting polymer formed by above-mentioned in-situ oxidation coupling reaction on the other hand can also play the effect of binding agent, strengthen the adhesion strength of anode.And, according to method of the present invention, even if add the additive of seldom amount in nonaqueous electrolytic solution, the effect of the high power discharge performance improving lithium rechargeable battery also can be obtained.
And prepared according to the methods of the invention lithium rechargeable battery also has high capacity and cycle performance.
In addition, method is simple according to of the present invention, is easy to accomplish scale production.
Embodiment
The invention provides a kind of preparation method of lithium rechargeable battery, the method comprises to be held Battery Pole Core in the cell housing, and nonaqueous electrolytic solution is injected in battery container, then the battery container of this injection nonaqueous electrolytic solution is carried out charging and change into rear sealing, wherein, described nonaqueous electrolytic solution contains additive, described additive is one or more in aniline system monomer and azole series monomer, described charging changes into and comprises one or more constant current charge, the charging current of at least one in this constant current charge is 0.001-0.05C, the cut-ff voltage that this charging changes into is 3.6-4.2V.
According to the inventive method, described nonaqueous electrolytic solution contains additive, described additive is oxidative coupling reaction can occur thus form the monomer of conducting polymer under electrochemical conditions, such as: described additive can be one or more in aniline system monomer and azole series monomer.In the present invention, the example of described additive can include but not limited to: aniline, o-aminoanisole, o-toluidine, m-toluidine, o ethyl aniline, o-chloraniline, adjacent fluoroaniline, methylphenylamine, N-ethylaniline, N-phenylaniline, benzidine, 2,5-dimethylaniline, pyrroles, 1-phenylpyrrole, 3-acetyl pyrrole, pyrroles-3-formic acid are (namely
), pyrroles-3-formaldehyde (that is,
), N-methylpyrrole, N-furfuryl group pyrroles, 3-amino-pyrroles, 3-methoxypyrrole, 1-(2-carbonyl benzene) pyrroles, 1-(3-bromopropyl) pyrroles, 1-(4-fluorophenyl) pyrroles, 1-(4-iodophenyl) pyrroles, pyrroles-3-Ethyl formate, 1-benzyl-3-cyanopyrrole, 3,4-ethyl dioxypyrrole (namely
), 1-(2-aminophenyl) pyrroles, 1-(2-nitrobenzyl) pyrroles, 1-(2-nitrobenzophenone) pyrroles, tosyl pyrroles, methylpyrrole-1-carboxylate (that is,
).Described additive is preferably aniline and/or pyrroles.From the further angle improving the electric conductivity of obtained lithium rechargeable battery, described additive is more preferably pyrroles.
In the present invention, the content of the additive in described nonaqueous electrolytic solution can carry out suitable selection according to the electric conductivity of expection.Preferably, with the total amount of described nonaqueous electrolytic solution for benchmark, the content of described additive is 0.01-10 % by weight.When the content of described additive is more than 0.01 % by weight, the effect of the electric conductivity improving lithium rechargeable battery further can be obtained; The content of described additive be not higher than 10 % by weight time, the effect of the electric conductivity significantly improving lithium rechargeable battery can be obtained, described additive effectively can also be avoided simultaneously to be polymerized the conducting polymer being formed and connect both positive and negative polarity in the electrolytic solution, and then to obtain the higher battery of security performance.From the further angle improving the electric conductivity of lithium rechargeable battery, with the total amount of described nonaqueous electrolytic solution for benchmark, the content of described additive is preferably 1-10 % by weight, is more preferably 3-10 % by weight, most preferably is 5-10 % by weight.
In the present invention, described nonaqueous electrolytic solution, except containing except additive, also contains electrolyte and organic solvent.
The various lithium salts that described electrolyte can be commonly used for this area, such as: lithium hexafluoro phosphate (LiPF
6), lithium perchlorate, LiBF4, hexafluoroarsenate lithium, lithium halide, chlorine lithium aluminate and fluorocarbon based Sulfonic Lithium.With the total amount of described nonaqueous electrolytic solution for benchmark, described electrolytical content can be 0.1-2mol/L, is preferably 0.5-1.5mol/L.
The various non-aqueous organic solvents that described organic solvent can be commonly used for this area.Such as, described organic solvent can be chain acid esters and ring-type acid esters mixed solution, and described chain acid esters can be dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), methyl propyl carbonate (MPC), dipropyl carbonate (DPC) and other is fluorine-containing, sulfur-bearing or containing at least one in the chain organosilane ester of unsaturated bond; Described ring-type acid esters can be ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton (γ-BL), sultone and other is fluorine-containing, sulfur-bearing or containing at least one in the ring-type organosilane ester of unsaturated bond.
According to method of the present invention, described nonaqueous electrolytic solution can also contain cosolvent, and described cosolvent is for improving the dissolubility of described additive in described nonaqueous electrolytic solution.The kind of described cosolvent can carry out suitable selection according to the kind of described additive.Preferably, described cosolvent can be one or more in toluene, nitrobenzene, dimethylbenzene, carbon tetrachloride and chloroform.In the present invention, the content of described cosolvent in described nonaqueous electrolytic solution can carry out suitable selection according to the consumption of the kind of described additive and described additive.Preferably, with the total amount of described nonaqueous electrolytic solution for benchmark, the content of described cosolvent is 0.1-15 % by weight.
According to the present invention, described charging changes into and can comprise one or more constant current charge, and the charging current of at least one in this constant current charge can be 0.001-0.05C.Preferably, the charging current of at least one in described constant current charge is 0.001-0.01C.Further preferably, the charging current of at least one in described constant current charge is 0.001-0.005C.
According to method of the present invention, the cut-ff voltage that described charging changes into can carry out suitable selection according to the kind of used additive, is as the criterion can make described additive generation oxidative coupling reaction.Usually, the cut-ff voltage that described charging changes into can be 3.6-5V.Preferably, the cut-ff voltage that described charging changes into is 3.6-4.2V.
According to the present invention, described charging changes into and preferably includes multiple constant current charge.The mode of described multiple constant current charge is preferably successively carries out the first constant current charge and the second constant current charge.The charging current of described first constant current charge can be 0.01-0.2C.The cut-ff voltage of described first constant current charge can be the oxidation voltage of described additive.Preferably, the cut-ff voltage of described first constant current charge is 2.5-3.6V.The charging current of described second constant current charge can be 0.001-0.05C, and the cut-ff voltage of described second constant current charge can be 3.6-4.2V.
Due to the additive in described nonaqueous electrolytic solution only reach its oxidation voltage after just there is oxidative coupling reaction, thus formation conducting polymer, therefore in the first constant current charge, adopt larger electric current to carry out the oxidation voltage of constant current charge to described additive, and then in the second constant current charge, adopt small area analysis to carry out constant current charge, to make described additive generation oxidative coupling reaction, can while acquisition has more excellent heavy-current discharge performance, further shortening changes into the time according to the charging of method of the present invention, and then obtain higher production efficiency.
In the second constant current charge, adopt higher than 0.05C electric current to the battery assembled carry out charging change into time, be difficult to the effect obtaining the electric conductivity improving lithium rechargeable battery, its reason may be: because current density is excessive, additive in nonaqueous electrolytic solution not yet moves to the surface of positive pole, just oxidative coupling reaction is there is in described nonaqueous electrolytic solution, form oligomer or polymer, above-mentioned oligomer or polymer are difficult to be attached on positive pole, play the effect of the conductivity improving positive electrode active materials.At the electric current that described charging changes into for during lower than 0.001C, then by extending the time of charging and changing into, cause production efficiency can not meet the demand of large-scale production.
Preferably, the charging current of described first constant current charge is 0.01-0.03C.
Preferably, the charging current of described second constant current charge is 0.001-0.01C.When adopting the electric current of 0.001-0.01C to charge in the second constant current charge, the additive in nonaqueous electrolytic solution can be made to be polymerized on positive pole more reposefully, and can not be polymerized in nonaqueous electrolytic solution, thus the heavy-current discharge performance that method according to the present invention is prepared into lithium ion can be improved further.Further preferably, the charging current of described second constant current charge is 0.001-0.005C.
In the present invention, the time (when comprising multiple constant current charge, the total time for multiple constant current charge) of described constant current charge can be 0.1-50 hour.
According to the present invention, described charging changes into and is also included in after described constant current charge completes, and carries out constant voltage charging.The voltage of described constant voltage charging is the cut-ff voltage of described constant current charge, when described constant current charge is multiple constant current charge, is the cut-ff voltage of last constant current charge.The time of described constant voltage charging can be 1 minute-3 hours, is preferably 30 minutes-3 hours, is more preferably 1-3 hour, more preferably 1.5-2.5 hour.
According to method of the present invention, charging changes into and can carry out under the charging of this area routine changes into temperature.Such as: described charging changes into temperature can be-40 DEG C to 100 DEG C, is preferably 20-60 DEG C.
Method according to the present invention is by adding in nonaqueous electrolytic solution by the additive that can form conducting polymer by oxidative coupling reaction under electrochemical conditions, and the lithium rechargeable battery containing above-mentioned nonaqueous electrolytic solution is charged under electric current is 0.001-0.05C, to carry out changing into the electric conductivity that improves the lithium rechargeable battery prepared by method of the present invention, therefore for pole piece in described lithium rechargeable battery, there is no particular limitation in the present invention, the pole piece can commonly used for this area.
Usually, described pole piece is made up of positive pole, negative pole and the barrier film between described positive pole and negative pole.
According to method of the present invention, the various methods that the preparation method of described positive pole can adopt this area conventional, such as can comprise positive active material, positive conductive agent and positive electrode binder and solvent, apply and/or be filled on positive electrode collector, dry, roll or do not roll, described positive pole can be obtained.
According to the present invention, described positive active material can adopt various positive active material well known in the art, such as LiCoO
2, LiVPO
4, LiCoAlO
2, LiMnCoO
2, LiCo
xni
ymn
zo
2(x+y+z=1), LiMn
2o
4, LiNiO
2and LiFe
xm
1-xpO
4one or more in (M is Co, Ni, Mn, 0.8≤x≤1).In the present invention, described positive active material can also be coated with carbon.In the present invention, the consumption of described positive active material can be the conventional amount used of this area.
Described positive conductive agent is not particularly limited, and can be the positive conductive agent of this area routine, such as: one or more in carbon black, graphite, acetylene black, carbon fiber, carbon nano-tube, carbonyl nickel powder, copper powder, iron powder, zinc powder and aluminium powder.In the present invention, the consumption of described conductive agent can be the conventional amount used of this area.
Described positive electrode binder can be the conventional various positive electrode binder in this area, such as: one or more in polyvinylidene fluoride, polytetrafluoroethylene, (fluorine-containing) polyacrylate, (fluorine-containing) polyurethane, (fluorine-containing) epoxy resin, butadiene-styrene rubber, poly-methylcellulose, poly-sodium carboxymethylcellulose pyce, hydroxypropyl methylcellulose and POLYPROPYLENE GLYCOL.
The solvent used when preparing positive pole can be the conventional various solvents in this area, such as can one or more for being selected from 1-METHYLPYRROLIDONE (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and alcohol series solvent.
The various positive electrode collectors that described positive electrode collector can be commonly used for this area, such as: aluminium foil.
Preparation in accordance with the present invention, the preparation method of described negative pole can be the conventional method of this area, such as can comprise: by negative electrode active material, cathode conductive agent and negative electrode binder and solvent, coating and/or filling are on the current collector, dry, roll or do not roll, described negative pole can be obtained.
Described negative electrode active material is not particularly limited, embedding and disengaging the negative electrode active material of lithium of this area routine can be used, such as: one or more in native graphite, natural modified graphite, Delanium, petroleum coke, organic cracking carbon, carbonaceous mesophase spherules, carbon fiber, ashbury metal and silicon alloy, preferred electrographite and natural modified graphite.
Described cathode conductive agent is not particularly limited, and can be the cathode conductive agent of this area routine, such as: one or more in ketjen carbon black, acetylene black, furnace black, carbon fiber VGCF, conductive carbon black and electrically conductive graphite.
The kind of described negative electrode binder and content are conventionally known to one of skill in the art, such as fluorine resin and/or polyolefin compound (as one or more in polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), butadiene-styrene rubber (SBR)).Described negative electrode binder adopts the mixture of cellulose-based polymer and rubber latex, as the mixture of cellulose-based polymer and butadiene-styrene rubber (SBR).The consumption of described cellulose-based polymer and butadiene-styrene rubber is conventionally known to one of skill in the art.
The solvent used when preparing negative pole can be selected from 1-METHYLPYRROLIDONE (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and alcohol series solvent one or more.The consumption of solvent can make described pastel have viscosity and mobility, can be coated on described collector body.
Described negative electrode collector can be negative electrode collector conventional in lithium ion battery, as stamped metal, and metal forming, net metal, foamed metal.
The method of described drying and calendering and condition are conventionally known to one of skill in the art, repeat no more herein.
The various barrier films that described barrier film can be commonly used for this area, such as polypropylene screen.
Method according to the present invention is carrying out before charging changes into, can also comprising and the battery container being injected with nonaqueous electrolytic solution being carried out ageing, fully infiltrate electrode active material in pole piece to make nonaqueous electrolytic solution.The present invention is not particularly limited for the condition of described ageing, can be the normal condition of this area.Such as, the condition of described ageing can be: temperature is 40-50 DEG C, is preferably 45 DEG C; Time is 20-30 hour, is preferably 24 hours.
Present invention also offers a kind of lithium rechargeable battery prepared by method of the present invention.The lithium rechargeable battery prepared by method of the present invention has the good and feature of the cycle performance excellence of battery of high power capacity, rate charge-discharge performance.
The present invention is described in detail below in conjunction with embodiment.
Embodiment 1
The present embodiment is used for illustrating according to lithium rechargeable battery of the present invention and preparation method thereof.
(1) preparation of positive pole
9g PVDF binding agent is joined in 170mL 1-METHYLPYRROLIDONE (NMP); after all dissolving; add 6g carbon black Super P conductive agent (being purchased from Shanghai Hui Pu industrial chemical Co., Ltd) and be uniformly dispersed, then by LiFePO coated for 150g carbon
4(carbon content 2.32 % by weight is purchased from Tianjin Yu Shun Science and Technology Ltd.) powder slowly joins in above-mentioned mixed solution, and high-speed stirred disperses 2 hours, obtained anode sizing agent.Be two-sided dressing on the aluminium foil of 16 microns at thickness, smear evenly.140 DEG C of oven dry, roll, rolling cut becomes positive plate, and pole piece size is 471cm (length) × 44cm (wide) × 0.0138cm (thick), and volume density is 2.3g/cm
3.
(2) preparation of negative pole
By Delanium (being purchased from Xinxiang Rightful Technology Co., Ltd.), carbon black Super P conductive agent (being purchased from Shanghai Hui Pu industrial chemical Co., Ltd), binding agent SBR (being purchased from Japanese A & L Co., Ltd.) and carboxymethyl cellulose (CMC) (being purchased from Shanghai ChangGuang Enterprises Development Co., Ltd) according to weight ratio 100: 2: 6: 2 Homogeneous phase mixing in deionized water.Be two-sided dressing on the Copper Foil of 10 microns at thickness, smear evenly.Dry at 120 DEG C, roll, rolling cut becomes positive plate, and pole piece size is 491cm (length) × 45cm (wide) × 0.0086 (thick), and volume density is 1.5g/cm
3.
(3) assembling of battery
Above-mentioned positive and negative electrode and polypropylene screen (being purchased from Japanese Asahi company) are wound into the pole piece of a square lithium ion battery, subsequently by LiPF
6be dissolved in the mixed solvent of EC: DEC: DMC=1: 1: 0.5 (weight ratio) by the concentration of 1 mol/L, and pyrroles is added in the mixed solution obtained, thus obtain nonaqueous electrolytic solution, wherein with the total amount of nonaqueous electrolytic solution for benchmark, the content of pyrroles is 5 % by weight.The nonaqueous electrolytic solution obtained is injected battery case with the amount of 6.5g/Ah.
(4) change into
Battery is placed 24 hours at the temperature of 50 DEG C, fully infiltrates electrode active material in pole piece to make nonaqueous electrolytic solution.Subsequently, battery is placed on formation cabinet, at 25 DEG C, first with 11mA (that is, electric current is for 0.02C) constant current charge to 3.6V, continue with the current strength of 2.75mA (namely, electric current is 0.005C) charging, cut-ff voltage 3.98V, constant voltage charge 2 hours, sealing, makes the lithium ion battery C1 that nominal capacity is 550 MAHs.
Comparative example 1
The method identical with embodiment 1 is adopted to prepare lithium rechargeable battery, unlike, do not use pyrroles, make the lithium rechargeable battery DC1 that nominal capacity is 550 MAHs.
Comparative example 2
(1) preparation of positive pole
The method identical with embodiment 1 is adopted to prepare positive pole, unlike, containing 0.36 gram of polypyrrole (business available from Aldrich Co, number-average molecular weight is 35000) in the positive pole slurries of preparation.
(2) preparation of negative pole
The method identical with embodiment 1 is adopted to prepare negative pole.
(3) assembling of battery
The method identical with embodiment 1 is adopted to carry out the assembling of battery, unlike, nonaqueous electrolytic solution is not containing pyrroles.
(4) change into
Adopt the condition identical with embodiment 1 to change into, make the lithium ion battery DC2 that nominal capacity is 550 MAHs.
Comparative example 3
The method identical with embodiment 1 is adopted to prepare lithium rechargeable battery, unlike, the condition changed into is: at 25 DEG C, with the current strength of 100mA (namely elder generation to 3.6V, continues with 50mA (that is, electric current is for 0.09C) constant current charge, electric current is 0.18C) overcharge, the degree of overcharging is 100% battery capacity, and sealing, makes the lithium ion battery DC3 that nominal capacity is 550 MAHs.
Embodiment 2
The present embodiment is used for illustrating according to lithium rechargeable battery of the present invention and preparation method thereof.
The method identical with embodiment 1 is adopted to prepare lithium rechargeable battery, unlike, the condition changed into is: at 25 DEG C, first with 11mA (that is, electric current is for 0.02C) constant current charge to 3.6V, continue with the current strength of 44mA (namely, electric current is 0.01C) charging, cut-ff voltage 3.98V, constant voltage charge 2 hours, sealing, makes the lithium ion battery C2 that nominal capacity is 550 MAHs.
Embodiment 3
The present embodiment is used for illustrating according to lithium rechargeable battery of the present invention and preparation method thereof.
The method identical with embodiment 1 is adopted to prepare lithium rechargeable battery, unlike, the condition changed into is: at 25 DEG C, first with 11mA (that is, electric current is for 0.02C) constant current charge to 3.6V, continue with the current strength of 0.55mA (namely, electric current is 0.001C) charging, cut-ff voltage 3.98V, constant voltage charge 2 hours, sealing, makes the lithium ion battery C3 that nominal capacity is 550 MAHs.
Embodiment 4
The present embodiment is used for illustrating according to lithium rechargeable battery of the present invention and preparation method thereof.
The method identical with embodiment 1 is adopted to prepare lithium rechargeable battery, unlike, with the total amount of nonaqueous electrolytic solution for benchmark, the content of pyrroles is 10 % by weight.Make the lithium rechargeable battery C4 that nominal capacity is 550 MAHs.
Embodiment 5
The present embodiment is used for illustrating according to lithium rechargeable battery of the present invention and preparation method thereof.
The method identical with embodiment 1 is adopted to prepare lithium rechargeable battery, unlike, with the total amount of nonaqueous electrolytic solution for benchmark, the content of pyrroles is 0.01 % by weight.Make the lithium rechargeable battery C5 that nominal capacity is 550 MAHs.
Embodiment 6
The present embodiment is used for illustrating according to lithium rechargeable battery of the present invention and preparation method thereof.
The method identical with embodiment 1 is adopted to prepare lithium rechargeable battery, unlike, the aniline of equal in quality is used to replace pyrroles, and toluene is added in nonaqueous electrolytic solution, with the total amount of described nonaqueous electrolytic solution for benchmark, the consumption of toluene is 7 % by weight, and when changing into, cut-ff voltage is 4.1V, makes the lithium rechargeable battery C6 that nominal capacity is 550 MAHs.
Embodiment 7
The present embodiment is used for illustrating according to lithium rechargeable battery of the present invention and preparation method thereof.
The method identical with embodiment 1 is adopted to prepare lithium rechargeable battery, unlike, adopt following methods to change into: to be placed 24 hours at the temperature of 50 DEG C by battery, fully infiltrate electrode active material in pole piece to make nonaqueous electrolytic solution.Subsequently, battery is placed on formation cabinet, at 25 DEG C, with the current strength of 2.75mA (that is, electric current is for 0.005C) constant current charge to 3.98V, then with the voltage constant voltage charge 2 hours of 3.98V, sealing, makes the lithium ion battery C7 that nominal capacity is 550 MAHs.
EXPERIMENTAL EXAMPLE 1-7
The performance of lithium rechargeable battery of EXPERIMENTAL EXAMPLE 1-7 for measuring embodiment 1-7 and preparing.
(1) multiplying power discharging property
Respectively lithium rechargeable battery prepared by above-described embodiment 1-7 is charged to 3.6V with the electric current of 0.2C, after shelving 10 minutes, respectively with the current discharge of 5C to 2.0V; Adopt same process, with the current discharge of 10C to 2.0V, with the current discharge of 15C to 2.0V, with the current discharge of 20C to 2.0V, with the current discharge of 25C to 2.0V, with the current discharge of 30C to 2.0V, and the every only each discharge capacity of record respectively.
Then calculate the ratio of the discharge capacity of each electric current and the current discharge capacity of 5C respectively, evaluate the multiplying power discharging property of battery with this, this ratio is larger, illustrates that multiplying power discharging property is better.The numerical value calculated illustrates in Table 1.
(2) mensuration of battery capacity
Respectively lithium rechargeable battery prepared by above-described embodiment 1-7 being charged to 3.6V with the constant current of 0.2C, with constant-potential charge after voltage rises to 3.6V, is 0.03C by electric current; Then discharging with the constant current of 0.2C, is 2.0V by voltage, measures the capacity of battery.Test result illustrates in table 2.
(3) mensuration of cycle performance of battery
Under 25 DEG C of conditions, respectively lithium rechargeable battery prepared by above-described embodiment 1-7 is charged to 3.6V with 1C electric current, with constant-potential charge after voltage rises to 3.6V, cut-off current is 0.03C, shelves 10 minutes; Again by battery with 1C current discharge to 2.0V, shelve 10 minutes.Be the initial capacity of this battery with the capacity of first charge-discharge, cycle-index when battery capacity is initial capacity 80% after record circulation.Test result illustrates in table 2.
Experimental comparison's example 1-3
The method identical with EXPERIMENTAL EXAMPLE 1-7 is adopted to measure the multiplying power discharging property of lithium rechargeable battery prepared by comparative example 1-3, battery capacity and cycle performance.Wherein, the test result of multiplying power discharging property illustrates in Table 1, and the test result of battery capacity and cycle performance illustrates in table 2.
Table 1
| 10C/5C(％) | 15C/5C(％) | 20C/5C(％) | 25C/5C(％) | 30C/5C(％) | |
| C1 | 0.99 | 0.97 | 0.94 | 0.88 | 0.80 |
| DC1 | 0.51 | 0.34 | 0.13 | 0.06 | 0.02 |
| DC2 | 0.65 | 0.52 | 0.38 | 0.23 | 0.09 |
| DC3 | 0.18 | 0.17 | 0.12 | 0.15 | 0.13 |
| C2 | 0.82 | 0.68 | 0.52 | 0.35 | 0.21 |
| C3 | 0.99 | 0.97 | 0.95 | 0.90 | 0.84 |
| C4 | 0.85 | 0.78 | 0.66 | 0.50 | 0.31 |
| C5 | 0.52 | 0.32 | 0.15 | 0.08 | 0.05 |
| C6 | 0.99 | 0.98 | 0.93 | 0.87 | 0.76 |
| C7 | 0.99 | 0.97 | 0.93 | 0.87 | 0.79 |
Table 2
| Initial capacity (mAh) | Cycle-index | |
| C1 | 552 | 2040 |
| DC1 | 532 | 531 |
| DC2 | 535 | 561 |
| DC3 | 17 | 23 |
| C2 | 546 | 1524 |
| C3 | 552 | 2521 |
| C4 | 552 | 1764 |
| C5 | 532 | 545 |
| C6 | 551 | 1954 |
| C7 | 552 | 2035 |
The result of table 1 shows, the lithium rechargeable battery prepared by method of the present invention has excellent multiplying power discharging property, particularly heavy-current discharge performance, illustrates that lithium rechargeable battery according to the present invention has good high power discharge performance.
The result of table 2 shows, prepares lithium rechargeable battery have high capacity and excellent cycle performance by method of the present invention.
Claims (9)
1. the preparation method of a lithium rechargeable battery, the method comprises to be held Battery Pole Core in the cell housing, and nonaqueous electrolytic solution is injected in battery container, then the battery container of this injection nonaqueous electrolytic solution is carried out charging and change into rear sealing, wherein, described nonaqueous electrolytic solution contains additive, described additive is one or more in aniline system monomer and azole series monomer, described charging changes into and comprises one or more constant current charge, the charging current of at least one in this constant current charge is 0.001-0.05C, the cut-ff voltage that this charging changes into is 3.6-4.2V.
2. method according to claim 1, wherein, with the total amount of described nonaqueous electrolytic solution for benchmark, the content of described additive is 0.01-10 % by weight.
3. method according to claim 2, wherein, with the total amount of described nonaqueous electrolytic solution for benchmark, the content of described additive is 5-10 % by weight.
4. according to the method in claim 1-3 described in any one, wherein, described additive is aniline and/or pyrroles.
5. method according to claim 1, wherein, the mode of described multiple constant current charge is for successively carrying out the first constant current charge and the second constant current charge, the condition of described first constant current charge comprises: charging current is 0.01-0.2C, and the cut-ff voltage of described first constant current charge is 2.5-3.6V; The condition of described second constant current charge comprises: charging current is 0.001-0.05C, and the cut-ff voltage of described second constant current charge is 3.6-4.2V.
6. method according to claim 5, wherein, the charging current of described second constant current charge is 0.001-0.01C.
7. method according to claim 1, wherein, described charging changes into and is also included in after described one or more constant current charge completes, carry out constant voltage charging, the voltage of described constant voltage charging is the cut-ff voltage of described constant current charge, and the time of described constant voltage charging is 1 minute-3 hours.
8. method according to claim 1, wherein, described nonaqueous electrolytic solution is also containing cosolvent, described cosolvent is one or more in toluene, nitrobenzene, dimethylbenzene, carbon tetrachloride and chloroform, with the total amount of described nonaqueous electrolytic solution for benchmark, the content of described cosolvent is 0.1-15 % by weight.
9. the lithium rechargeable battery prepared by the method in claim 1-8 described in any one.
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| US7358012B2 (en) | 2004-01-06 | 2008-04-15 | Sion Power Corporation | Electrolytes for lithium sulfur cells |
| KR20130105839A (en) | 2010-08-24 | 2013-09-26 | 바스프 에스이 | Electrolyte materials for use in electrochemical cells |
| US8735002B2 (en) | 2011-09-07 | 2014-05-27 | Sion Power Corporation | Lithium sulfur electrochemical cell including insoluble nitrogen-containing compound |
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| US9577289B2 (en) | 2012-12-17 | 2017-02-21 | Sion Power Corporation | Lithium-ion electrochemical cell, components thereof, and methods of making and using same |
| WO2015149345A1 (en) * | 2014-04-04 | 2015-10-08 | Basf Corporation | Lithium-ion batteries and preparation method thereof |
| CN103928714B (en) * | 2014-04-30 | 2017-03-22 | 安普瑞斯（无锡）有限公司 | Method for in-situ polymerization of conductive polyaniline in lithium ion battery pole group |
| US9831488B1 (en) * | 2016-12-11 | 2017-11-28 | StoreDot Ltd. | In-battery polymerization of conducting polymers for high-rate charging cathodes |
| US10593946B2 (en) | 2016-12-11 | 2020-03-17 | StoreDot Ltd. | LFP as initiator of in-battery polymerization of conducting polymers for high-rate-charging cathodes |
| CN106532121B (en) * | 2016-12-23 | 2019-05-21 | 厦门大学 | It is a kind of reduce lithium-air battery charging overpotential electrolysis additive and its application |
| CN107887649A (en) * | 2017-10-19 | 2018-04-06 | 江西恒动新能源有限公司 | An a kind of two formation charging processes of power lithium-ion battery series connection |
| JP6897601B2 (en) * | 2018-02-23 | 2021-06-30 | トヨタ自動車株式会社 | Manufacturing method of solid rechargeable battery system |
| CN109346763B (en) * | 2018-10-19 | 2021-01-05 | 惠州市豪鹏科技有限公司 | Electrolyte and lithium ion battery |
| CN111384457A (en) * | 2018-12-28 | 2020-07-07 | 安普瑞斯（南京）有限公司 | Formation method for improving first charge-discharge efficiency of lithium ion battery |
| CN112563571A (en) * | 2019-09-26 | 2021-03-26 | 宁德时代新能源科技股份有限公司 | Additive for battery, secondary battery, battery module, battery pack and device |
| CN111916837B (en) * | 2020-08-14 | 2021-11-30 | 江苏中奕和创智能科技有限公司 | Formation method of lithium-nickel-based composite compound battery |
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